WO2018182226A1

WO2018182226A1 - Redox flow battery

Info

Publication number: WO2018182226A1
Application number: PCT/KR2018/003277
Authority: WO
Inventors: 정현진; 김대식; 최원석; 김태언; 정진교; 서동균; 김진후
Original assignee: 롯데케미칼 주식회사
Priority date: 2017-03-30
Filing date: 2018-03-21
Publication date: 2018-10-04
Also published as: KR20180110792A

Abstract

One aspect of the present invention provides a redox flow battery for minimizing the level difference of an electrolyte in an electrolyte tank, the level difference occurring due to a difference, in viscosity and specific gravity of the electrolyte, generated during charging and discharging. According to one embodiment of the present invention, the redox flow battery comprises: a stack module including unit stacks in which an anode electrolyte and a cathode electrolyte internally flows so as to generate an electric current; and a heat exchanger provided at an anode electrolyte outflow line through which the anode electrolyte of the stack module flows out, wherein the heat exchanger can comprise: a first chamber and a second chamber spaced apart from each other so as to allow the anode electrolyte to flow in and discharge the same; and a flow path for connecting the first chamber and the second chamber so as to circulate the anode electrolyte therethrough.

Description

Redox flow battery

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a redox flow cell, and more particularly, to a redox flow cell cooling a high temperature electrolyte flowing out after a reaction in a stack with a heat exchanger.

Zinc bromine redox flow cells are a type of flow cells that produce electricity through redox reactions between the electrolyte and the electrodes.

For example, a redox flow battery is formed by repeatedly stacking a bipolar electrode and a membrane, stacking current collector plates and end caps on both sides of the outermost layer, and supplying electrolyte to oxidize the electrolyte. A stack in which a reduction reaction occurs, a pump and a pipe for supplying an electrolyte solution to the stack, and an electrolyte tank for storing the electrolyte solution flowing out after the internal reaction in the stack.

The electrolyte tank comprises an anode electrolyte tank containing an anode electrolyte containing zinc, a cathode electrolyte tank containing a cathode electrolyte containing bromine, and a two-phase electrolyte tank containing two phases of the cathode electrolyte ( 230).

The redox flow cell further includes a water-cooled or air-cooled heat exchanger for cooling the hot electrolyte flowing out after the reaction in the stack. The heat exchanger may increase heat exchange performance by increasing the surface area of the heat exchange and the path of the electrolyte. The flow of the electrolyte varies according to the internal structure of the heat exchanger, and the internal pressure changes.

However, in order to increase the heat exchange performance, excessively increasing the surface area of the heat exchange and the path of the electrolyte, crossover of the electrolyte in the stack due to the difference in the viscosity and specific gravity of the electrolyte generated during charging and discharging, the anode electrolyte tank and the cathode electrolyte tank Level difference between electrolytes occurs. For this reason, charge quantity efficiency falls and energy efficiency falls.

Embodiments of the present invention to provide a redox flow battery that minimizes the difference in the level of the electrolyte in the electrolyte tank generated due to the difference in viscosity and specific gravity of the electrolyte generated during charging and discharging.

In addition, embodiments of the present invention to provide a redox flow battery that improves heat exchange performance while optimizing energy efficiency.

Redox flow battery according to an embodiment of the present invention, a stack module including a unit stack for generating a current, an electrolyte tank for storing an electrolyte solution supplied to the stack module and outflow from the stack module, the electrolyte tank in the An electrolyte inflow line for introducing electrolyte into the stack module, an electrolyte outflow line for outflowing the electrolyte from the stack module to the electrolyte tank, and a heat exchanger provided at an anode electrolyte outflow line for outflowing an anode electrolyte from the electrolyte outflow line The heat exchanger is spaced apart from each other to form a first chamber and a second chamber for inflow and outflow of the anode electrolyte, and a flow path for circulating the anode electrolyte by connecting the first chamber and the second chamber to be exposed to the outside air flow. May comprise tubes.

The first chamber is connected to the electrolyte outlet line to the inlet port for introducing the anode electrolyte, the outlet port connected to the electrolyte outlet line for outflow of the anode electrolyte, and is disposed between the inlet port and the outlet port It may include a septum partitioning both sides of the first sub-chamber and the second sub-chamber.

The anode electrolyte may include the inflow port of the first chamber, the first sub chamber, a portion of the tubes, the second chamber, another portion of the tubes, the second sub chamber of the first chamber, and the It may be via the outlet port of the first chamber.

The first chamber is connected to the electrolyte outlet line to inlet the anode electrolyte inlet, connected to the electrolyte outlet line outlet port for outflowing the anode electrolyte, and the inlet port from the inlet port sequentially arranged And an eleventh diaphragm and a twelfth diaphragm for dividing the eleventh subchamber, the twelfth subchamber, and the thirteenth subchamber.

The second chamber may include a twenty-first sub-chamber connected to the eleventh sub-chamber and the twelfth sub-chamber as part of the tubes, and another part of the tubes to the twelfth and thirteenth sub-chambers. It may include a second diaphragm for partitioning the 22nd sub-chamber.

The first chamber has an inflow port connected to the electrolyte outflow line for introducing the anode electrolyte, and the second chamber has an outflow port connected to the electrolyte outflow line for outflowing the anode electrolyte. The port and the outlet port may be arranged to form a maximum distance from the first chamber and the second chamber.

The first chamber may include a first diaphragm which is disposed on the inlet port side to define a fourteenth subchamber and a fifteenth subchamber larger than the fourteenth subchamber.

The second chamber may include a second diaphragm which is disposed on the outlet port side to define a twenty-fourth sub-chamber and a twenty-fifth sub-chamber larger than the twenty-fourth sub-chamber.

The twenty-fourth sub-chamber may be connected to some of the tubes to the fifteenth sub-chamber, and the twenty-fifth sub-chamber may be connected to another portion of the tubes to the fourteenth and sixteenth sub-chambers.

Embodiments of the present invention are provided with a heat exchanger in the anode electrolyte outflow line for outflowing the anode electrolyte is less reactive than the cathode electrolyte, and cools the anode electrolyte heated by the reaction, due to the difference in viscosity and specific gravity of the electrolyte during charging and discharging Crossover of the electrolyte in the generated stack is reduced, thereby minimizing the level difference of the electrolyte in the anode electrolyte tank and the cathode electrolyte tank. That is, the charge quantity efficiency is high, and consequently the energy efficiency can be optimized.

1 is a block diagram of a redox flow battery according to an embodiment of the present invention.

FIG. 2 is a perspective view illustrating a stack module, an electrolyte tank, and a heat exchanger applied to FIG. 1.

3 is an exploded perspective view of a unit module applied to FIG. 2.

4 is a cross-sectional view taken along line IV-IV of FIG. 3.

5 is a cross-sectional view taken along the line VV of FIG. 3.

FIG. 6 is a perspective view illustrating a heat exchanger of a first embodiment applied to FIG. 2.

7 is a cross-sectional view taken along the line VII-VII of FIG. 6.

FIG. 8 is a cross-sectional view of the heat exchanger of the second embodiment applied to FIG. 2.

FIG. 9 is a cross-sectional view of the heat exchanger of the third embodiment applied to FIG. 2.

FIG. 10 is a cross-sectional view of the heat exchanger of the fourth embodiment applied to FIG. 2.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like elements throughout the specification.

Throughout the specification, when a part is "connected" to another part, it includes not only "directly connected", but also "indirectly connected" between other members. In addition, when a part is said to "include" a certain component, this means that it may further include other components, except to exclude other components unless otherwise stated.

When a part of a layer, a film, an area, a plate, etc. in the specification is said to be "on" or "on" another part, it is not only when it is "right on" the other part but also when there is another part in the middle. Include. And "on" or "on" means to be located above or below the target portion, and does not necessarily mean to be located above the gravity direction.

1 is a block diagram of a redox flow battery according to an embodiment of the present invention, Figure 2 is a perspective view showing a stack module, an electrolyte tank and a heat exchanger applied to FIG. 1 and 2, the redox flow battery of one embodiment supplies an electrolyte to a stack module 120 and a stack module 120 that generate current and store an electrolyte flowing out of the stack module 120. Tank 200.

The stack module 120 includes a plurality of unit modules 110. As an example, the stack module 120 is formed by arranging two unit modules 110 on the side of each other and electrically connecting them. The unit module 110 is configured to generate a current in the circulation of the electrolyte, and as an example, includes four

unit stacks

101, 102, 103, and 104, respectively.

For example, the electrolyte tank 200 includes an anode electrolyte tank 210 containing an anode electrolyte containing zinc, a cathode electrolyte tank 220 containing a cathode electrolyte containing bromine, and a cathode electrolyte two phases. It includes a two-phase electrolyte tank 230 for receiving.

In addition, the redox flow battery of the embodiment is connected to the electrolyte tank 200 and the stack module 120, the electrolyte inflow line (La1 Lc1) flowing the electrolyte into the stack module 120 by the driving of the electrolyte pump (Pa, Pc) ), And electrolyte solution outlet lines La2 and Lc2 connecting the electrolyte tank 200 and the stack module 120 to discharge the electrolyte solution from the stack module 120.

The redox flow battery of one embodiment includes a heat exchanger 600 in the anode electrolyte outflow line La2 for outflowing the anode electrolyte from the electrolyte outflow lines La2 and Lc2. The heat exchanger 600 is disposed on the side of the anode electrolyte which is less reactive than the cathode electrolyte, and directly contacts the anode electrolyte to consider the efficiency of the battery.

In addition, during charging and discharging, crossover of the electrolyte occurs in the stack module 120 due to differences in viscosity and specific gravity of the electrolyte. This may cause a difference in water level between the anode electrolyte tank 210 and the cathode electrolyte tank 220.

The heat exchanger 600 is configured to minimize the difference in the water level of the electrolyte. The structure and arrangement of the heat exchanger 600 increases the efficiency of the redox flow cell and enables the durability and long term cycle stability of the stack module 120. As an example, the heat exchanger 600 may be air cooled to minimize power consumption. Although not shown, a fan that forms an air flow in the heat exchanger 600 may be provided at one side of the heat exchanger 600.

3 is an exploded perspective view of a unit module applied to FIG. 2. 1 to 3, the anode electrolyte tank 210 is an anode between the membrane electrode 10 and the anode electrode 32 of the

unit stacks

101, 102, 103, 104 forming the unit module 110. The electrolyte is supplied and the anode electrolyte flowing out between the membrane 10 and the anode electrode 32 is accommodated.

The cathode electrolyte tank 220 accommodates the cathode electrolyte supplied between the membrane 10 of the unit stacks 101, 102, 103, 104 forming the unit module 110 and the cathode electrode 31, and the anode electrolyte The tank 210 is connected to the first overflow pipe 201. The first overflow tube 201 allows the electrolyte of the anode and

cathode electrolyte tanks

210 and 220 to be exchanged with each other.

The two-phase electrolyte tank 230 is a cathode electrolyte (aqueous bro) flowing out between the membrane electrode 10 and the cathode electrode 31 of the unit stacks 101, 102, 103, 104 forming the unit module 110. An electrolyte containing two phases of min and heavy mixed bromine) and is connected to the cathode electrolyte tank 220 by a second overflow tube 202. In addition, a lower portion of the two-phase electrolyte tank 230 and a lower portion of the cathode electrolyte tank 220 are connected to the communication tube 203.

The two-phase electrolyte tank 230 separates the cathode electrolyte flowing out between the membrane 10 and the cathode electrode 31 into two phases according to specific gravity, that is, accommodates the mixed bromine on the lower side and the aqueous bromine on the upper side. To accept. Aqueous bromine is supplied to the cathode electrolyte tank 220 through the second overflow tube 202.

That is, the second overflow tube 202 is supplied with the upper aqueous bromine to the cathode electrolyte tank 220. During discharge, the lower heavy mixed bromine may be supplied between the membrane 10 and the cathode electrode 31 in place of the cathode electrolyte of the cathode electrolyte tank 220 through the communication tube 203.

To this end, the electrolyte inflow lines La1 and Lc1 are the anode electrolyte inflow line La1 connecting the anode electrolyte tank 210 to the unit module 110 and the stack module 120, and during discharge, the two-phase electrolyte tank ( 230 or at the time of filling, the cathode electrolyte inlet line Lc1 connecting the cathode electrolyte tank 220 to the unit module 110 and the stack module 120.

The electrolyte outflow lines La2 and Lc2 are the anode electrolyte outflow line La2 connecting the anode electrolyte tank 210 to the unit module 110 and the stack module 120, and the unit module 110 and the stack module 120. It includes a cathode electrolyte outflow line (Lc2) connecting the two-phase electrolyte tank (230).

The anode and cathode electrolyte inflow lines La1 and Lc1 are connected to the anode electrolyte tank 210 and the cathode electrolyte tank through the electrolyte inlets H21 and H31 of the unit module 110 via the anode and cathode electrolyte pumps Pa and Pc. And 220 or two-phase electrolyte tank 230, respectively. The anode and cathode electrolyte outlet lines La2 and Lc2 connect the anode electrolyte tank 210 and the two-phase electrolyte tank 230 to the electrolyte outlets H22 and H32 of the unit module 110, respectively.

The anode electrolyte tank 210 contains an anode electrolyte containing zinc, and drives the anode electrolyte between the membrane 10 of the unit module 110 and the anode electrode 32 by driving the anode electrolyte pump Pa. Circulate

The cathode electrolyte tank 220 or the two-phase electrolyte tank 230 contains a cathode electrolyte containing bromine, and the membrane 10 and the cathode of the unit module 110 are driven by the cathode electrolyte pump Pc. The cathode electrolyte is circulated between the electrodes 31.

In addition, the two-phase electrolyte tank 230 drives the cathode electrolyte flowing out between the membrane 10 of the unit module 110 and the cathode electrode 31 by the driving of the cathode electrolyte pump Pc to the cathode electrolyte outlet line Lc2. Depending on the difference in specific gravity, the mixture receives the mixed bromine on the lower side and the aqueous bromine on the upper side.

Meanwhile, the cathode electrolyte inlet line Lc1 connects the cathode electrolyte tank 220 and the two-phase electrolyte tank 230 to the stack module 120 via the cathode electrolyte pump Pc, and the cathode electrolyte outlet line Lc2. The silver stack module 120 connects to the two-phase electrolyte tank 230 and the cathode electrolyte tank 220. Therefore, the inflow and outflow operation of the cathode electrolyte to the stack module 120 may be performed.

The communication tube 203 may be provided with an intermittent valve (not shown), and may drive the cathode electrolyte pump Pc during discharge to supply the cathode electrolyte of the two-phase electrolyte tank 230 to the stack module 120. That is, when the intermittent valve is closed during charging, the cathode electrolyte of the cathode electrolyte tank 220 is supplied to the cathode electrolyte inflow line Lc1. When the intermittent valve is opened during discharge, the cathode electrolyte of the two-phase electrolyte tank 230 is cathode. It is supplied to the electrolyte inflow line Lc1.

In addition, the unit stacks 101, 102, 103, 104 are electrically connected to each other through bus bars B1 and B2. The unit module 110 and the stack module 120 discharge current generated in the unit stacks 101, 102, 103, and 104 through the busbars B1 and B2, or are connected to an external power supply to the anode. The electrolyte tank 210 and the two-phase electrolyte tank 230 may be charged with current.

The unit modules 110 are formed by stacking the unit stacks 101, 102, 103, and 104 as shown in FIG. 2. Since the unit modules 110 are disposed on the side of each other, the stack module 120 is formed.

In the unit module 110, electrolyte inlets H21 and H31 are provided in the left unit cell C1 (see FIG. 3), and the electrolyte inlets H21 and H31 are provided through the anode and cathode electrolyte pumps Pa and Pc. The anode and cathode electrolyte inflow lines La1 and Lc1 are respectively connected to the anode electrolyte tank 210 and the cathode electrolyte tank 220 or the two-phase electrolyte tank 230.

In addition, the electrolyte module outlets H22 and H32 are provided at the right side unit cell C2 in the unit module 110 (see FIG. 3), and the electrolyte outlets H22 and H32 are anode and cathode electrolyte outlet lines La2 and Lc2. And are connected to the anode electrolyte tank 210 and the two-phase electrolyte tank 230, respectively.

The electrolyte inlets H21 and H31 flow the electrolyte from the anode electrolyte tank 210, the cathode electrolyte tank 220, or the two-phase electrolyte tank 230 into the left unit cell C1, respectively (see FIG. 3). The electrolyte outlets H22 and H32 flow out the electrolyte from the right unit cell C2 (see FIG. 3) through the unit module 110 to the anode electrolyte tank 210 and the two-phase electrolyte tank 230, respectively. do.

4 is a cross-sectional view taken along line IV-IV of FIG. 3, and FIG. 5 is a cross-sectional view taken along line V-V of FIG. 3. 3 to 5, the unit module 110 may include a membrane 10, a spacer 20, an electrode plate 30, a flow frame (eg, a membrane flow frame 40, and an electrode flow frame 50). ), And the unit stacks 101, 102, 103, and 104 including the first and

second collector plates

61 and 62 and the first and second end caps 71 and 72 are repeatedly stacked. .

Referring to the unit module 110, since the unit stacks 101, 102, 103, and 104 have two unit cells C1 and C2, one electrode flow frame 50 is provided at the center, and Two membrane flow frames 40 arranged in both symmetrical structures on both sides of the flow frame 50, and two first and second end caps 71 and 72 disposed respectively outside the membrane flow frame 40. It includes.

The membrane 10 is configured to pass ions and is coupled to the membrane flow frame 40 at the center of the thickness direction of the membrane flow frame 40. The electrode plate 30 is coupled to the electrode flow frame 50 at the center of the thickness direction of the electrode flow frame 50.

The first end cap 71, the membrane flow frame 40, the electrode flow frame 50, the membrane flow frame 40 and the second end cap 72 are disposed, and the membrane 10 and the electrode plate 30 are disposed. By joining the membrane flow frame 40, the electrode flow frame 50, and the first and second end caps 71 and 72 to each other via the spacer 20 therebetween, the two unit cells C1 and C2 are joined. Unit stacks 101, 102, 103, and 104 are formed.

The electrode plate 30 forms the anode electrode 32 on one side and the cathode electrode 31 on the other side at the portion where the two unit cells C1 and C2 are connected, thereby forming the two unit cells C1 and C2. To form a bipolar electrode connecting in series.

The membrane flow frame 40, the electrode flow frame 50, and the first and second end caps 71 and 72 are bonded to each other to establish an internal volume S between the membrane 10 and the electrode plate 30. And first and second channel channels CH1 (see FIG. 4) and CH2 (see FIG. 5) for supplying an electrolyte solution to the internal volume S. The first and second flow channels CH1 and CH2 are configured to supply the electrolyte at uniform pressure and amount on both sides of the membrane 10, respectively.

The membrane flow frame 40, the electrode flow frame 50, and the first and second end caps 71 and 72 may be formed of an electrical insulating material including a synthetic resin component, and may be bonded by thermal fusion or vibration fusion.

The first flow channel CH1 connects the electrolyte inlet H21, the internal volume S and the electrolyte outlet H22 to drive the membrane 10 and the anode electrode 32 by driving the anode electrolyte pump Pa. The anode electrolyte is introduced into the internal volume S set therebetween to allow flow out after the reaction (see FIG. 4).

The second channel CH2 connects the electrolyte inlet H31, the internal volume S and the electrolyte outlet H32, and drives the membrane 10 and the cathode electrode 31 by driving the cathode electrolyte pump Pc. The cathode electrolyte is introduced into the internal volume S set therebetween to allow flow out after the reaction (see FIG. 5).

The anode electrolyte is redox-reacted at the anode electrode 32 side of the internal volume S to generate a current and stored in the anode electrolyte tank 200. The cathode electrolyte is redox-reacted on the cathode electrode 31 side of the internal volume S to generate a current and stored in the two-phase electrolyte tank 230.

During charging, between the membrane 10 and the cathode electrode 31,

2Br ^{^-} → 2Br + 2e ^- (formula 1)

As a chemical reaction occurs, bromine included in the cathode electrolyte is produced and stored in the two-phase electrolyte tank 230. At this time, bromine is immediately mixed by the tetraammonium ions in the cathode electrolyte to form a high density second phase which is immediately removed from the unit module 110, such as the cathode electrolyte. The aqueous bromine separated in the two-phase electrolyte tank 230 is overflowed to the cathode electrolyte tank 220 through the second overflow tube 202.

During charging, between the membrane 10 and the anode electrode 32,

Zn ²⁺ + 2e ^- → Zn (Equation 2)

As a chemical reaction occurs, zinc contained in the anode electrolyte is deposited and stored on the anode electrode 32. In this case, the anode electrolyte or the cathode electrolyte between the anode electrolyte tank 210 and the cathode electrolyte tank 220 may overflow each other through the first overflow pipe 201.

During discharge, a reverse reaction of equation 1 occurs between the membrane 10 and the cathode electrode 31, and a reverse reaction of equation 2 occurs between the membrane 10 and the anode electrode 32.

The first and second

current collector plates

61 and 62 collect current generated from the cathode electrode 31 and the anode electrode 32 or supply current to the cathode electrode 31 and the anode electrode 32 from the outside. The

outermost electrode plates

30 and 30 are bonded to and electrically connected to each other.

Discharge currents generated in the unit stacks 101, 102, 103, 104, the unit module 110, and the stack module 120, or are connected to an external power source to the anode electrolyte tank 210 and the two-phase electrolyte tank 230. ) Needs to be charged with current.

To this end, the first end cap 71 is integrally formed by receiving the first collector plate 61 to which the bus bar B1 is connected, and the electrode plate 30 connected to the first collector plate 61. One side of the unit stacks 101, 102, 103, and 104 is formed. The second end cap 72 is integrally formed to accommodate the second collector plate 62 to which the bus bar B2 is connected, and the electrode plate 30 connected to the second collector plate 62. The other one outer side of 101, 102, 103, 104 is formed.

The first end cap 71 includes anode and cathode electrolyte inlets H21 and H31 at one side thereof, and is connected to the first and second channel CHs CH1 and CH2, respectively, to introduce the cathode electrolyte and the anode electrolyte. The second end cap 72 has electrolyte outlets H22 and H32 on one side thereof, and is connected to the first and second channel channels CH1 and CH2 to respectively discharge the cathode electrolyte and the anode electrolyte.

That is, the cathode electrolyte flowing out through the cathode electrolyte outflow line Lc2 flows into the two-phase electrolyte tank 230. Therefore, the mixed bromine mixed in the cathode electrolyte introduced into the two-phase electrolyte tank 230 is located below.

Therefore, the overflow from the two-phase electrolyte tank 230 to the second overflow pipe 202 is an aqueous bromine located on the upper side, and the heavy mixed bromine located on the lower side does not overflow.

During charging, the intermittent valve is closed to supply the cathode electrolyte from the cathode electrolyte tank 220 to the cathode electrolyte inflow line Lc1. At this time, the two-phase electrolyte tank 230 accommodates the cathode electrolyte.

At the time of discharge, the cathode electrolyte is supplied from the cathode electrolyte tank 220 to the cathode electrolyte inflow line Lc1. In addition, the discharge valve is opened during discharge to supply the cathode electrolyte containing the mixed bromine to the cathode electrolyte inlet line (Lc1).

FIG. 6 is a perspective view illustrating a heat exchanger of a first embodiment applied to FIG. 2. Referring to FIG. 6, the heat exchanger 600 of the first embodiment is connected to the anode electrolyte outlet line La2 and is spaced apart from each other by the first chamber 610 and the second chamber 620, and the first and second chambers. The

tubes

630 and 620 are connected to each other to form tubes 630 for forming a flow path for circulating the anode electrolyte.

The anode electrolyte flowing out of the anode electrolyte outlet line La2 flows into any one side of the first and

second chambers

610 and 620, and is heat exchanged through the tubes 630, and then flows to the same side or the other side. Spills.

In the first embodiment, after the reaction, the heated anode electrolyte flows into the first chamber 610 and flows back to the first chamber 610 via the tubes 630 and the second chamber 620, the outside of the Heat exchange in tubes 630 exposed to the air stream. The number of tubes 630 is set in consideration of the viscosity and specific gravity of the electrolyte.

7 is a cross-sectional view taken along the line VII-VII of FIG. 6. Referring to FIG. 7, the first chamber 610 includes an inlet port 611, an outlet port 612, and a diaphragm 613. The diaphragm 613 is disposed between the inlet port 611 and the outlet port 612 to partition the first chamber 610 into the first sub chamber 614 and the second sub chamber 615. The internal flow path set as the diaphragm 613 and the tubes 630 has a curved structure in consideration of the heat exchange area and the internal pressure.

The inlet port 611 is connected to the anode electrolyte outlet line La2 to inject the anode electrolyte into the first sub chamber 614, and the outlet port 612 is connected to the anode electrolyte outlet line La2 to the second sub chamber. The anode electrolyte flows out from 615. That is, the inlet port 611 and the outlet port 612 are located on the same side in the first chamber 610.

After the reaction, the anode electrolyte that is heated and flows out to the anode electrolyte outlet line La2 may be a portion of the inlet port 611 of the first chamber 610, the first sub chamber 614, the tubes 630, and the second chamber. 620, another portion of the tubes 630, via the second sub chamber 615 of the first chamber 610, and the outlet port 612 of the first chamber 610. That is, the first and

second chambers

610 and 620 and the tube 630 increase the heat exchange surface area and the path of the electrolyte at an appropriate ratio.

Therefore, since the anode electrolyte passing through the heat exchanger 600 is cooled, the difference in viscosity and specific gravity that may occur during charging and discharging is minimized, thereby minimizing crossover that may occur in the stack module 120. . Therefore, the difference in the level of the electrolyte in the anode electrolyte tank 210 and the cathode electrolyte tank 220 may be minimized.

Hereinafter, various embodiments of the present invention will be described. Compared to the first embodiment and the previously described embodiment, the same configuration is omitted, and different configurations will be described.

FIG. 8 is a cross-sectional view of the heat exchanger of the second embodiment applied to FIG. 2. Referring to FIG. 8, in the heat exchanger 700 of the second embodiment, the first chamber 710 includes an inlet port 711, an outlet port 712, an eleventh diaphragm 713, and a twelfth diaphragm 714. Include. The eleventh diaphragm 713 and the twelfth diaphragm 714 are sequentially disposed from the inflow port 711 to the outflow port 712, and the first chamber 710 is disposed in the eleventh sub chamber 715 and the twelfth sub. The chamber 716 and the thirteenth subchamber 717 are partitioned.

The inlet port 711 is connected to the anode electrolyte outlet line La2 to introduce the anode electrolyte into the eleventh subchamber 715, and the outlet port 712 is connected to the anode electrolyte outlet line La2 to the thirteenth subchamber. The anode electrolyte flows out from 717.

The second chamber 720 includes a second diaphragm 723. The second diaphragm 723 divides the second chamber 720 into a twenty-first sub chamber 721 and a twenty-second sub chamber 722. The twenty-first sub-chamber 721 is connected to the eleventh sub-chamber 715 and the twelfth sub-chamber 716 as part of the tubes 730, and the twenty-second sub-chamber 722 is connected to the twelfth sub-chamber 716. The thirteenth subchamber 717 is connected to another part of the tubes 730.

After the reaction, the anode electrolyte that is heated and flows out to the anode electrolyte outlet line La2 may be a portion of the inlet port 711 of the first chamber 710, the eleventh subchamber 715, the tubes 730, and the second chamber. The twenty-first sub chamber 721 of 720, a portion of the tubes 730, the twelfth sub chamber 716 of the first chamber 710, a portion of the tubes 730, and a second chamber 720 of the second chamber 720. The twenty-second sub chamber 722, some of the tubes 730, the thirteenth sub chamber 717 of the first chamber 710, and the outlet port 712 are provided. That is, when compared with the first embodiment, the first,

second chambers

710 and 720 and the tube 730 are identical to each other in the heat exchange surface area, and are further increased in the path of the electrolyte.

Therefore, looking at Table 1 below, the second embodiment forms a larger temperature difference between the inlet port 711 and the outlet port 712 than the first embodiment, but shows a larger difference in the level of the electrolyte. For this reason, the second embodiment has lower energy efficiency than the first embodiment.

FIG. 9 is a cross-sectional view of the heat exchanger of the third embodiment applied to FIG. 2. Referring to FIG. 9, in the heat exchanger 800 of the third embodiment, the first chamber 810 is provided with an inlet port 811 connected to the anode electrolyte outlet line La2 and introducing the anode electrolyte, and a second The chamber 820 is connected to the anode electrolyte outlet line La2 and has an outlet port 821 for outflowing the anode electrolyte.

The first and

second chambers

810 and 820 are connected to the tubes 830, and the inflow port 811 and the outflow port 821 have a maximum distance from the first chamber 810 and the second chamber 820. Formed and placed.

After the reaction, the anode electrolyte that is heated and flows out to the anode electrolyte outlet line La2 is inlet port 811, first chamber 810, tubes 730, and second chamber 820 of the first chamber 810. And via an outlet port 821 of the second chamber 820. That is, the first,

second chambers

810, 820 and the tube 830 are the same in the heat exchange surface area, and further reduced in the path of the electrolyte when compared with the first embodiment.

Therefore, referring to Table 1 below, the third embodiment forms a similar temperature difference between the inlet port 811 and the outlet port 812 compared to the first embodiment, but has a larger difference in the level of the electrolyte (second embodiment). Although the water level difference is smaller than the example). For this reason, the third embodiment showed lower energy efficiency (higher energy efficiency than the second embodiment) than the first embodiment.

FIG. 10 is a cross-sectional view of the heat exchanger of the fourth embodiment applied to FIG. 2. Referring to FIG. 10, in the heat exchanger 900 of the fourth embodiment, the first chamber 910 includes a first diaphragm 912. The first diaphragm 912 is disposed to be inclined toward the inlet port 911 and divided into a fourteenth subchamber 914 and a fifteenth subchamber 915. The fifteenth subchamber 915 is larger than the fourteenth subchamber 914.

The second chamber 920 includes a second diaphragm 922. The second diaphragm 922 is disposed to face the outlet port 921 and is divided into a twenty-fourth sub chamber 924 and a twenty-fifth sub chamber 925. The twenty-fifth sub-chamber 925 is larger than the twenty-fourth sub-chamber 924.

The twenty-fourth subchamber 924 is connected to the fifteenth subchamber 915 as part of the tubes 930, and the twentyfifth subchamber 925 is connected to the fourteenth subchamber 914 and the fifteenth subchamber 915. To another part of the tubes 930.

After the reaction, the anode electrolyte that is heated and flows out to the anode electrolyte outlet line La2 is inlet port 911, the fourteenth subchamber 914, the tubes 930, and the second chamber 920 of the first chamber 910. 24th subchamber 924 of the 25th subchamber 925, the tubes 930, the 15th subchamber 915 of the first chamber 910, the tubes 930, and the second chamber 920. And through the outlet port 921. That is, the first,

second chambers

910, 920 and the tube 930 are the same in the heat exchange surface area, and are further increased in the path of the electrolyte as compared with the third embodiment.

Therefore, in Table 1 below, the fourth embodiment has an increased temperature difference between the inlet port 911 and the outlet port 921 (the temperature difference is lower than that of the second embodiment), compared to the third embodiment. Shows the opposite difference in water level. For this reason, the fourth embodiment showed slightly lower energy efficiency than the third embodiment (the energy efficiency is higher than that of the second embodiment).

The experimental results of the redox flow batteries applying the same flow rate to the first to fourth embodiments are shown in Table 1.

동일한 유속Same flow rate	제1실시예First embodiment	제2실시예Second embodiment	제3실시예Third embodiment	제4실시예Fourth embodiment
전해액의 수위 비율(애노드 전해액: 캐소드 전해액)Water level ratio of electrolyte solution (anode electrolyte: cathode electrolyte)	(55:45)(55:45)	(25:75)(25:75)	(65:35)(65:35)	(35:65)(35:65)
온도 차이(열교환기의 유입포트와 유출포트)(℃)Temperature difference (inlet and outlet ports of the heat exchanger) (℃)	2.52.5	33	2.42.4	2.82.8
에너지 효율(%)Energy efficiency (%)	72.772.7	68.268.2	70.570.5	69.769.7

Comparing the second, third and fourth embodiments with the first embodiment, the temperature difference between the inlet port 611 and the outlet port 612 of the heat exchanger 600 is 2.5 ° C. However, in the first embodiment, the energy level ratio of the electrolyte is 55:45, that is, the difference in the level of the anode and cathode electrolytes is smallest as 10, compared to the other second, third, and fourth embodiments. The highest was 72.7%.

As such, the anode electrolyte heated by the reaction is cooled by a heat exchanger (600, 700, 800, 900), so that when the charge and discharge, the crossover of the electrolyte in the stack module 120 due to the difference in viscosity and specific gravity of the electrolyte Decreases.

For this reason, the level difference between the electrolytes in the anode electrolyte tank 210 and the cathode electrolyte tank 220 may be minimized. The heat exchanger 600 of the first embodiment has higher charge quantity efficiency and, consequently, more energy efficiency than the

heat exchangers

700, 800, 900 of the other second, third, and fourth embodiments. Can be.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Description of the sign

10: membrane 20: spacer

30: electrode plate 31: cathode electrode

32: anode electrode 40: membrane flow frame

50: electrode flow frame 61, 62: first, second collector plate

71, 72: first and

second end cap

101, 102, 103, 104: unit stack

110: unit module 120: stack module

200: electrolyte tank 201: first overflow tube

202: second overflow pipe 203: communication pipe

210: anode electrolyte tank 220: cathode electrolyte tank

230: two-

phase electrolyte tank

600, 700, 800, 900: heat exchanger

610, 710, 810, 910:

first chamber

611, 711, 811, 911: inlet port

612, 712, 821, 921: outlet port 613: diaphragm

614: first sub chamber 615: second sub chamber

620, 720, 820, 920:

second chamber

630, 730, 830, 930: tube

713: Eleventh diaphragm 714: 12th diaphragm

715: 11th subchamber 716: 12th subchamber

717: thirteenth subchamber 721: twenty-first subchamber

722: 22nd subchamber 723: second diaphragm

912: first diaphragm 914: 14th subchamber

915: 15th subchamber 922: second diaphragm

924: 24th subchamber 925: 25th subchamber

B1, B2: Busbars C1, C2: Unit cells

CH1, CH2: first and second channel H21, H31: electrolyte inlet

H22, H32: electrolyte outlet La1 Lc1: electrolyte inlet line

La2, Lc2: electrolyte outflow line Pa, Pc: electrolyte pump

S: internal volume

Claims

A stack module including unit stacks in which an anode electrolyte and a cathode electrolyte flow and generate current; And

And a heat exchanger provided at an anode electrolyte outlet line through which the anode electrolyte solution of the stack module flows out.

The heat exchanger,

A first chamber and a second chamber spaced apart from each other to allow the anode electrolyte to flow in and out;

A flow path for circulating an anode electrolyte by connecting the first chamber and the second chamber

Redox flow battery comprising a.
The method of claim 1,

The flow path connecting the first chamber and the second chamber includes a tube exposed to the outside air flow.
The method of claim 2,

The first chamber is

An inlet port connected to the anode electrolyte outlet line for introducing the anode electrolyte;

An outlet port connected to the anode electrolyte outlet line for outflowing the anode electrolyte solution, and

The diaphragm is disposed between the inlet port and the outlet port to partition both sides into a first sub chamber and a second sub chamber.

Redox flow battery comprising a.
The method of claim 3,

The anode electrolyte is

The inlet port of the first chamber, the first sub chamber, part of the tubes, the second chamber, another part of the tubes, the second sub chamber of the first chamber and the first chamber of the first chamber. Redox flow cell via outlet port.
The method of claim 2,

The first chamber is

An inlet port connected to the anode electrolyte outlet line for introducing the anode electrolyte;

An outlet port connected to the anode electrolyte outlet line for outflowing the anode electrolyte solution, and

The 11th diaphragm and the 12th diaphragm which are arranged sequentially from the inflow port to the outflow port and partition 11th sub chamber, 12th sub chamber, and 13th sub chamber

Redox flow battery comprising a.
The method of claim 5,

The second chamber is

A twenty-first sub chamber connected to the eleventh sub chamber and the twelfth sub chamber by a part of the tubes;

And a second diaphragm which defines a twenty-second sub chamber connected to the twelfth sub chamber and the thirteenth sub chamber by another part of the tubes.
The method of claim 2,

The first chamber is

It is connected to the anode electrolyte outlet line having an inlet port for introducing the anode electrolyte,

The second chamber is

It is connected to the anode electrolyte outlet line and has an outlet port for outflowing the anode electrolyte,

The inlet port and the outlet port

Redox flow battery disposed to form a maximum distance from the first chamber and the second chamber.
The method of claim 7, wherein

The first chamber is

Redox flow battery comprising a first diaphragm disposed on the inlet port side and partitioning a 14th subchamber and a 15th subchamber larger than the 14th subchamber.
The method of claim 8,

The second chamber is

And a second diaphragm disposed on the outlet port side to define a twenty-fourth sub-chamber and a twenty-fifth sub-chamber larger than the twenty-fourth sub-chamber.
The method of claim 9,

The twenty-fourth subchamber is connected to the fifteenth subchamber by some of the tubes,

The 25th subchamber is connected to the 14th subchamber and the 15th subchamber with a redox flow battery.